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© Author(s) 2019. This work is distributed under
the Creative Commons Attribution 4.0 License.
© Author(s) 2019. This work is distributed under
the Creative Commons Attribution 4.0 License.

Research article 24 May 2019

Research article | 24 May 2019

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This discussion paper is a preprint. It is a manuscript under review for the journal Atmospheric Chemistry and Physics (ACP).

Alkyl nitrates in the boreal forest: Formation via the NO3, OH and O3 induced oxidation of BVOCs and ambient lifetimes

Jonathan Liebmann1, Nicolas Sobanski1, Jan Schuladen1, Einar Karu1, Heidi Hellén2, Hannele Hakola2, Qiaozhi Zha3, Mikael Ehn3, Matthieu Riva4, Jonathan Williams1, Horst Fischer1, Jos Lelieveld1, and John N. Crowley1 Jonathan Liebmann et al.
  • 1Division of Atmospheric Chemistry, Max Planck Institut für Chemie, 55128, Mainz, Germany
  • 2Finnish Meteorological Institute, 00560, Helsinki, Finland
  • 3Institute for Atmospheric and Earth System Research/Physics, University of Helsinki, 00014, Helsinki, Finland
  • 4University of Lyon, Université Claude Bernard Lyon1, CNRS, IRCELYON, 69626, Villeurbanne, France

Abstract. The formation of alkyl nitrates in various oxidation processes taking place throughout the diel cycle can represent an important sink of reactive nitrogen and mechanism for chain-termination in atmospheric photo-oxidation cycles. The low volatility alkyl nitrates formed from biogenic volatile organic compounds (BVOCs), especially terpenoids, enhance rates of production and growth of secondary organic aerosol. Measurements of the NO3-reactivity and the mixing ratio of total alkyl nitrates in the Finnish boreal forest enabled assessment of the relative importance of NO3, O3 and OH-initiated formation of alkyl-nitrates from BVOCs in this environment. The high reactivity of the forest air towards NO3 resulted in reactions of the nitrate radical with terpenes contributing substantially to formation of ANs not only during the night but also during daytime. Overall, night-time reactions of NO3 accounted for 49 % of the local production rate of ANs, with contributions of 21 %, 18 % and 12 % for NO3, OH and O3, during the day. The lifetimes of the gas-phase ANs formed in this environment were of the order of 2 hours implying that the lifetime of NOx is strongly controlled by biogenic emissions from the forest. As the organic nitrates are lost to the particle phase and via dry-deposition to foliar surfaces, the overall result is transfer of reactive nitrogen from anthropogenic sources to the forest ecosystem.

Jonathan Liebmann et al.
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Jonathan Liebmann et al.
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Short summary
The formation of alkyl nitrates in the boreal forest was dominated by reactions of the NO3 radical with terpenes, both during the day and the night, with lesser contributions from OH and ozone. The Alkyl nitrates formed had lifetimes on the order of two hours, reflecting efficient loss via uptake to aerosol and deposition.
The formation of alkyl nitrates in the boreal forest was dominated by reactions of the NO3...